Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004133/ta1289sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004133/ta1289Isup2.hkl |
CCDC reference: 147606
The organolanthanide complex described in this paper is very sensitive to air and moisture. Consequently, all manipulations were carried out under argon by Schlenk techniques. Crystals of (I) were obtained by the reaction of YbCp'3 with one equivalent of isopropyl alcohol in tetrahydrofuran, followed by crystallization from a toluene solution at 263 K. A suitable crystal was sealed in a thin-walled glass capillary for single-crystal structure determination.
H atoms were included but not refined. Please provide full details of C—H distances, etc. All calculations were performed using the TEXSAN (1992b) crystallographic software package. Full reference?
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I) showing 40% probability displacement ellipsoids. H atoms are omitted for clarity. |
[Y2(C6H7)4(C3H7O)2] | Dx = 1.385 Mg m−3 |
Mr = 612.46 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8370 (8) Å | Cell parameters from 4567 reflections |
b = 12.3820 (9) Å | θ = 2.4–26.0° |
c = 12.1515 (9) Å | µ = 3.96 mm−1 |
β = 97.212 (2)° | T = 298 K |
V = 1468.36 (19) Å3 | Prismatic, colourless |
Z = 2 | 0.50 × 0.35 × 0.30 mm |
F(000) = 632 |
Siemens SMART CCD area detector query diffractometer | 3002 independent reflections |
Radiation source: fine-focus sealed tube | 2484 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scan | θmax = 26.4°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.132, Tmax = 0.305 | k = −9→15 |
6773 measured reflections | l = −14→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0628P)2] where P = (Fo2 + 2Fc2)/3 |
3002 reflections | (Δ/σ)max = 0.002 |
154 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.82 e Å−3 |
[Y2(C6H7)4(C3H7O)2] | V = 1468.36 (19) Å3 |
Mr = 612.46 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8370 (8) Å | µ = 3.96 mm−1 |
b = 12.3820 (9) Å | T = 298 K |
c = 12.1515 (9) Å | 0.50 × 0.35 × 0.30 mm |
β = 97.212 (2)° |
Siemens SMART CCD area detector query diffractometer | 3002 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2484 reflections with I > 2σ(I) |
Tmin = 0.132, Tmax = 0.305 | Rint = 0.033 |
6773 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.89 e Å−3 |
3002 reflections | Δρmin = −0.82 e Å−3 |
154 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Y1 | 0.02541 (3) | 1.01773 (2) | 0.35923 (2) | 0.03312 (12) | |
O1 | 0.10623 (18) | 0.92928 (16) | 0.51278 (15) | 0.0353 (4) | |
C1 | 0.2088 (4) | 0.8509 (3) | 0.5487 (4) | 0.0751 (12) | |
H1A | 0.2027 | 0.8442 | 0.6283 | 0.090* | |
C2 | 0.1750 (4) | 0.7413 (3) | 0.5057 (3) | 0.0626 (10) | |
H2A | 0.0808 | 0.7257 | 0.5121 | 0.094* | |
H2B | 0.2326 | 0.6896 | 0.5479 | 0.094* | |
H2C | 0.1898 | 0.7375 | 0.4292 | 0.094* | |
C3 | 0.3497 (3) | 0.8873 (4) | 0.5450 (5) | 0.0859 (14) | |
H3A | 0.3605 | 0.9591 | 0.5748 | 0.129* | |
H3B | 0.3693 | 0.8873 | 0.4696 | 0.129* | |
H3C | 0.4119 | 0.8394 | 0.5883 | 0.129* | |
C4 | 0.1296 (4) | 1.1536 (3) | 0.2205 (3) | 0.0656 (11) | |
H4A | 0.1025 | 1.1558 | 0.1401 | 0.079* | |
C5 | 0.0752 (4) | 1.2181 (3) | 0.2958 (4) | 0.0722 (12) | |
H5A | 0.0064 | 1.2747 | 0.2779 | 0.087* | |
C6 | 0.1542 (4) | 1.2051 (3) | 0.3947 (4) | 0.0691 (11) | |
H6A | 0.1491 | 1.2508 | 0.4598 | 0.083* | |
C7 | 0.2574 (4) | 1.1315 (3) | 0.3846 (3) | 0.0647 (10) | |
H7A | 0.3367 | 1.1178 | 0.4401 | 0.078* | |
C8 | 0.2428 (4) | 1.0969 (3) | 0.2729 (4) | 0.0644 (10) | |
C9 | 0.3347 (6) | 1.0209 (4) | 0.2209 (6) | 0.0996 (19) | |
H9A | 0.4074 | 1.0610 | 0.1940 | 0.149* | |
H9B | 0.2828 | 0.9838 | 0.1602 | 0.149* | |
H9C | 0.3730 | 0.9693 | 0.2751 | 0.149* | |
C10 | −0.1942 (4) | 0.9093 (4) | 0.2691 (3) | 0.0758 (13) | |
H10A | −0.2837 | 0.9090 | 0.2966 | 0.091* | |
C11 | −0.0918 (5) | 0.8327 (3) | 0.2942 (3) | 0.0709 (12) | |
H11A | −0.0984 | 0.7694 | 0.3418 | 0.085* | |
C12 | 0.0053 (4) | 0.8477 (3) | 0.2254 (3) | 0.0657 (10) | |
H12A | 0.0798 | 0.7972 | 0.2163 | 0.079* | |
C13 | −0.0340 (4) | 0.9318 (4) | 0.1564 (3) | 0.0610 (10) | |
H13A | 0.0096 | 0.9521 | 0.0912 | 0.073* | |
C14 | −0.1591 (5) | 0.9728 (3) | 0.1825 (3) | 0.0643 (11) | |
C15 | −0.2409 (7) | 1.0634 (5) | 0.1224 (5) | 0.127 (3) | |
H15A | −0.3017 | 1.0342 | 0.0617 | 0.191* | |
H15B | −0.1795 | 1.1139 | 0.0944 | 0.191* | |
H15C | −0.2933 | 1.0996 | 0.1728 | 0.191* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Y1 | 0.04355 (18) | 0.02590 (18) | 0.03048 (17) | −0.00484 (11) | 0.00682 (11) | 0.00056 (10) |
O1 | 0.0384 (10) | 0.0291 (11) | 0.0382 (10) | 0.0050 (8) | 0.0036 (8) | 0.0020 (8) |
C1 | 0.057 (2) | 0.049 (2) | 0.117 (4) | 0.0144 (18) | 0.002 (2) | 0.005 (2) |
C2 | 0.078 (3) | 0.043 (2) | 0.068 (2) | 0.0250 (18) | 0.0126 (19) | −0.0035 (18) |
C3 | 0.041 (2) | 0.080 (3) | 0.135 (4) | 0.0178 (19) | 0.005 (2) | 0.026 (3) |
C4 | 0.081 (3) | 0.059 (2) | 0.058 (2) | −0.018 (2) | 0.018 (2) | 0.023 (2) |
C5 | 0.088 (3) | 0.035 (2) | 0.100 (3) | −0.0030 (19) | 0.038 (3) | 0.017 (2) |
C6 | 0.089 (3) | 0.046 (2) | 0.078 (3) | −0.032 (2) | 0.032 (2) | −0.011 (2) |
C7 | 0.055 (2) | 0.065 (3) | 0.076 (3) | −0.0277 (19) | 0.0128 (18) | 0.011 (2) |
C8 | 0.064 (2) | 0.049 (2) | 0.089 (3) | −0.0143 (18) | 0.044 (2) | 0.002 (2) |
C9 | 0.102 (4) | 0.090 (4) | 0.120 (5) | 0.001 (3) | 0.062 (4) | −0.002 (3) |
C10 | 0.061 (2) | 0.103 (4) | 0.064 (2) | −0.034 (2) | 0.0093 (19) | −0.039 (3) |
C11 | 0.108 (3) | 0.042 (2) | 0.057 (2) | −0.026 (2) | −0.015 (2) | −0.0039 (18) |
C12 | 0.089 (3) | 0.042 (2) | 0.063 (2) | 0.0100 (19) | −0.003 (2) | −0.0197 (19) |
C13 | 0.092 (3) | 0.054 (3) | 0.0377 (17) | 0.000 (2) | 0.0076 (18) | −0.0162 (16) |
C14 | 0.079 (3) | 0.058 (2) | 0.049 (2) | 0.0082 (19) | −0.021 (2) | −0.0175 (19) |
C15 | 0.156 (6) | 0.101 (4) | 0.105 (4) | 0.055 (4) | −0.062 (4) | −0.020 (4) |
Y1—O1 | 2.2228 (19) | C1—C3 | 1.464 (5) |
Y1—O1i | 2.2432 (18) | C1—C2 | 1.477 (5) |
Y1—C11 | 2.641 (4) | C4—C5 | 1.373 (6) |
Y1—C6 | 2.652 (4) | C4—C8 | 1.400 (5) |
Y1—C12 | 2.653 (3) | C5—C6 | 1.356 (6) |
Y1—C10 | 2.660 (3) | C6—C7 | 1.381 (6) |
Y1—C5 | 2.661 (4) | C7—C8 | 1.414 (6) |
Y1—C7 | 2.667 (3) | C8—C9 | 1.499 (6) |
Y1—C4 | 2.675 (3) | C10—C11 | 1.390 (6) |
Y1—C13 | 2.680 (3) | C10—C14 | 1.391 (6) |
Y1—C8 | 2.683 (3) | C11—C12 | 1.359 (6) |
Y1—C14 | 2.690 (4) | C12—C13 | 1.362 (6) |
O1—C1 | 1.428 (4) | C13—C14 | 1.404 (6) |
O1—Y1i | 2.2432 (18) | C14—C15 | 1.514 (6) |
O1—Y1—O1i | 74.86 (7) | C13—Y1—C8 | 82.99 (13) |
Cp1—Y1—Cp2 | 124.0 | O1—Y1—C14 | 134.64 (11) |
O1—Y1—C11 | 85.43 (10) | O1i—Y1—C14 | 102.92 (11) |
O1i—Y1—C11 | 101.11 (12) | C11—Y1—C14 | 49.94 (13) |
O1—Y1—C6 | 100.45 (12) | C6—Y1—C14 | 124.83 (14) |
O1i—Y1—C6 | 86.39 (10) | C12—Y1—C14 | 49.88 (12) |
C11—Y1—C6 | 171.54 (13) | C10—Y1—C14 | 30.14 (13) |
O1—Y1—C12 | 96.59 (10) | C5—Y1—C14 | 95.27 (15) |
O1i—Y1—C12 | 130.70 (11) | C7—Y1—C14 | 133.11 (14) |
C11—Y1—C12 | 29.75 (13) | C4—Y1—C14 | 84.29 (14) |
C6—Y1—C12 | 142.30 (14) | C13—Y1—C14 | 30.31 (12) |
O1—Y1—C10 | 106.47 (13) | C8—Y1—C14 | 104.74 (15) |
O1i—Y1—C10 | 85.62 (10) | C1—O1—Y1 | 139.1 (2) |
C11—Y1—C10 | 30.39 (14) | C1—O1—Y1i | 115.7 (2) |
C6—Y1—C10 | 148.76 (16) | Y1—O1—Y1i | 105.14 (7) |
C12—Y1—C10 | 49.66 (13) | O1—C1—C3 | 114.7 (3) |
O1—Y1—C5 | 130.01 (13) | O1—C1—C2 | 113.4 (3) |
O1i—Y1—C5 | 94.08 (10) | C3—C1—C2 | 116.3 (4) |
C11—Y1—C5 | 144.24 (14) | C5—C4—C8 | 110.1 (4) |
C6—Y1—C5 | 29.57 (13) | C5—C4—Y1 | 74.5 (2) |
C12—Y1—C5 | 124.39 (14) | C8—C4—Y1 | 75.17 (19) |
C10—Y1—C5 | 121.38 (17) | C6—C5—C4 | 107.1 (4) |
O1—Y1—C7 | 87.28 (10) | C6—C5—Y1 | 74.8 (2) |
O1i—Y1—C7 | 108.98 (11) | C4—C5—Y1 | 75.6 (2) |
C11—Y1—C7 | 145.92 (15) | C5—C6—C7 | 110.2 (4) |
C6—Y1—C7 | 30.09 (13) | C5—C6—Y1 | 75.6 (2) |
C12—Y1—C7 | 119.16 (14) | C7—C6—Y1 | 75.6 (2) |
C10—Y1—C7 | 162.42 (13) | C6—C7—C8 | 107.3 (4) |
C5—Y1—C7 | 49.84 (14) | C6—C7—Y1 | 74.4 (2) |
O1—Y1—C4 | 135.55 (10) | C8—C7—Y1 | 75.3 (2) |
O1i—Y1—C4 | 123.58 (11) | C4—C8—C7 | 105.3 (4) |
C11—Y1—C4 | 123.00 (13) | C4—C8—C9 | 127.6 (5) |
C6—Y1—C4 | 48.65 (13) | C7—C8—C9 | 127.0 (5) |
C12—Y1—C4 | 96.77 (14) | C4—C8—Y1 | 74.54 (19) |
C10—Y1—C4 | 114.42 (14) | C7—C8—Y1 | 74.06 (18) |
C5—Y1—C4 | 29.82 (12) | C9—C8—Y1 | 119.2 (3) |
C7—Y1—C4 | 49.50 (13) | C11—C10—C14 | 108.1 (4) |
O1—Y1—C13 | 126.14 (11) | C11—C10—Y1 | 74.1 (2) |
O1i—Y1—C13 | 132.49 (10) | C14—C10—Y1 | 76.1 (2) |
C11—Y1—C13 | 49.01 (13) | C12—C11—C10 | 108.5 (4) |
C6—Y1—C13 | 122.76 (13) | C12—C11—Y1 | 75.6 (2) |
C12—Y1—C13 | 29.59 (12) | C10—C11—Y1 | 75.5 (2) |
C10—Y1—C13 | 49.38 (12) | C11—C12—C13 | 108.4 (4) |
C5—Y1—C13 | 97.51 (15) | C11—C12—Y1 | 74.7 (2) |
C7—Y1—C13 | 113.62 (12) | C13—C12—Y1 | 76.3 (2) |
C4—Y1—C13 | 74.15 (13) | C12—C13—C14 | 109.1 (4) |
O1—Y1—C8 | 106.83 (11) | C12—C13—Y1 | 74.08 (19) |
O1i—Y1—C8 | 136.22 (10) | C14—C13—Y1 | 75.2 (2) |
C11—Y1—C8 | 122.66 (14) | C10—C14—C13 | 105.9 (4) |
C6—Y1—C8 | 49.91 (12) | C10—C14—C15 | 128.1 (5) |
C12—Y1—C8 | 92.99 (14) | C13—C14—C15 | 125.9 (5) |
C10—Y1—C8 | 132.02 (13) | C10—C14—Y1 | 73.8 (2) |
C5—Y1—C8 | 50.33 (12) | C13—C14—Y1 | 74.5 (2) |
C7—Y1—C8 | 30.64 (12) | C15—C14—Y1 | 119.8 (3) |
C4—Y1—C8 | 30.29 (12) |
Symmetry code: (i) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Y2(C6H7)4(C3H7O)2] |
Mr | 612.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.8370 (8), 12.3820 (9), 12.1515 (9) |
β (°) | 97.212 (2) |
V (Å3) | 1468.36 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.96 |
Crystal size (mm) | 0.50 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector query diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.132, 0.305 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6773, 3002, 2484 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.099, 1.09 |
No. of reflections | 3002 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.89, −0.82 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Y1—O1 | 2.2228 (19) | Y1—C5 | 2.661 (4) |
Y1—O1i | 2.2432 (18) | Y1—C7 | 2.667 (3) |
Y1—C11 | 2.641 (4) | Y1—C4 | 2.675 (3) |
Y1—C6 | 2.652 (4) | Y1—C13 | 2.680 (3) |
Y1—C12 | 2.653 (3) | Y1—C8 | 2.683 (3) |
Y1—C10 | 2.660 (3) | Y1—C14 | 2.690 (4) |
O1—Y1—O1i | 74.86 (7) | Y1—O1—Y1i | 105.14 (7) |
Cp1—Y1—Cp2 | 124.0 |
Symmetry code: (i) −x, −y+2, −z+1. |
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The lanthanide alkoxides have been used in a variety of applications, including as homogeneous catalysts for organic synthesis and polymerization (Shibasaki et al., 1997; Shen et al., 1995) and in the preparation of high purity oxide materials (Hubert-Pfalzgraf, 1995). In our study of the catalytic properties of organolanthanide alkoxides the title complex, (I), was obtained from the reaction of Cp'3Y (Cp'= CH3C5H4) with an equimolar amount of isopropyl alcohol in tetrahydrofuran. \sch
In the crystal, (I) is found to be a centrosymmetric binuclear molecule, with the isopropoxide ligands as the bridging groups. This is similar to other binuclear bis(cyclopentadienyl) lanthanide alkoxides (Wu et al., 1994, 1992; Evans et al., 1986). The eight-coordinate metal centres are coordinated to two methylcyclopentadienyl ring centroids and two O atoms of the isopropoxide ligands, to form a distorted tetrahedral geometry.
The Y1—O1 [2.2228 (19) Å] distance in (I) is much longer than that observed for the Yb—O bond [2.1970 (5) Å] in [(C5H5)2Yb(µ-OCH2CH2CH3)]2 (Wu et al., 1992) and a little shorter than the Y—O bond [2.275 (3) Å] in [(MeC5H4)2Y(µ-OCH=CH2)] (Evans et al., 1986), but is similar to the value accepted for the Y—O bond [2.2170 (3) Å] in [(C5H4SiMe3)2Y(µ-OMe)]2 (Evans et al., 1992). The bond angle O1—Y1—O1(-x, 2 − y, 1 − z) [74.86 (7)°] in (I) is slightly larger than those found in related complexes, such as [(C5H5)2Yb(µ-OCH2CH2CH3)]2 [73.6 (2)°; Wu et al., 1992], [(MeC5H4)2Y(µ-OCH=CH2)]2 [73.1 (7)°; Evans et al., 1986] and [(C5H4SiMe3)2Y(µ-OMe)]2 [73.6 (1)°; Evans et al., 1992]. However, the bond angle Y—O—Y(-x, 2 − y, 1 − z) [105.14 (7)°] is much smaller than those found in the corresponding related (Cp'2LnOR)2 structures (Ln = ?), such as [(MeC5H4)2Y(µ-OCH=CH2)]2 [106.9 (1)°; Evans et al., 1986] and [(C5H4SiMe3)2Y(µ-OMe)]2 [106.4 (1)°; Evans et al., 1992].